TW202218887A - Decorative sheet and decorative material - Google Patents

Abstract

Provided are a decorative sheet and a decorative material having both excellent antiviral properties and high processability. This decorative sheet is provided with a colored layer, a patterned layer and a surface protective layer, wherein: the surface protective layer comprises a first surface protective layer containing an antiviral agent together with at least one of a heat-curable resin, an ultraviolet ray-curable resin and an electron beam-curable resin; the addition amount of the antiviral agent is 0.2-10 mass% inclusive relative to the surface protective layer; and the average particle size of the antiviral agent is 1-10 [mu]m inclusive.

Description

Decorative sheets and decorative materials

This disclosure relates to decorative sheets and decorative materials.

Conventionally, the decorative sheet that can be imparted with antiviral properties by adding an antiviral agent has the following problem: most of the antiviral agent is kneaded into the resin and entered into the molded article, so it cannot be expressed on the surface. Antiviral effect. In this regard, a decorative sheet having excellent antiviral properties by adding an antiviral agent to the outermost surface of the decorative sheet has been proposed (for example, refer to Patent Document 1). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-080887

[The problem to be solved by the invention]

In addition, when an antiviral agent is kneaded into a molding resin or a coating resin, there is a problem that, for example, the suitability of the decorative sheet (eg, bending workability) tends to decrease.

An object of the present disclosure is to provide a decorative sheet and a decorative material having excellent antiviral properties and high suitability for processability. [means to solve the problem]

In order to solve the above-mentioned problems, a decorative sheet according to an aspect of the present disclosure is characterized by comprising a colored layer, a pattern layer, and a surface protective layer, wherein the surface protective layer has an antiviral agent, a thermosetting resin, and an ultraviolet curing type. The first surface protective layer of at least one of resins or electron beam curable resins has an added amount of the antiviral agent relative to the surface protective layer of 0.2 mass % or more and 10 mass % or less, and the average particle diameter of the antiviral agent It is 1 μm or more and 10 μm or less. [Effect of invention]

According to the decorative sheet of one aspect of the present disclosure, a decorative sheet and a decorative material with high scratch resistance and virus resistance can be provided.

[Form for carrying out the invention]

An embodiment of the present disclosure will be described with reference to the drawings. Here, the configuration shown in the drawings is a schematic configuration, and the relationship between the thickness and the plane size, the ratio of the thickness of each layer, and the like are different from the actual configuration. In addition, the embodiment shown below is an example of the structure for embodying the technical idea of this disclosure, and the material, shape, structure, etc. of the technical idea of this disclosure are not limited to the following. Various changes can be added to the technical idea of the present disclosure within the technical scope specified by the claims described in the scope of the patent application.

<First Embodiment> (Composition of decorative sheet) The basic structure of the decorative sheet according to the first embodiment of the present disclosure will be described with reference to FIG. 1 . FIG. 1 is a cross-sectional view for explaining a configuration example of the decorative sheet 10 according to the first embodiment of the present disclosure. As shown in FIG. 1 , the decorative sheet 10 according to an embodiment of the present disclosure is attached to one side of the colored layer 12 , and a pattern layer 13 and a surface protection layer 14 are laminated in this order. Moreover, the surface protection layer 14 has the 1st surface protection layer 14a, and the 2nd surface protection layer 14b. Hereinafter, each layer will be described in detail.

(colored layer) The colored layer 12 is a layer that becomes the base material of the decorative sheet 10 . In the present embodiment, a thermoplastic resin can be used as the colored layer 12 . The thermoplastic resin is not particularly limited, and for example, polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, and propylene-α-olefin copolymer can be used and other polyolefin resins, or ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene-(meth)acrylic acid (ester) copolymers, ethylene-unsaturated carboxylic acid copolymers metal neutralized products (ionic compounds) ) and other olefin-based copolymer resins and other polyolefin-based resins, or polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate (polytetramethylene terephthalate), polynaphthalene ethylene terephthalate, polyethylene terephthalate-isophthalate copolymer, 1,4-cyclohexanedimethanol copolymer polyethylene terephthalate, polyarylate, polycarbonate Polyester resins such as esters, acrylic acids such as poly(meth)acrylonitrile, polymethyl(meth)acrylate, polyethyl(meth)acrylate, polybutyl(meth)acrylate, polyacrylamide, etc. Polyamide resins such as 6-nylon, 6,6-nylon, and 6,10-nylon, styrene resins such as polystyrene, AS resin, and ABS resin, polyvinyl chloride, polyvinyl acetate , polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral and other vinyl resins, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, ethylene-perfluoroalkyl ethylene Fluorine-based resins such as base ether copolymers, or the like, or mixtures, copolymers, composites, laminates, and the like of two or more of them.

Here, many thermoplastic resins have been mentioned as thermoplastic resins that can be used for the colored layer 12. However, in consideration of the recent rise in social concerns about environmental issues, chlorine (halogen)-containing resins such as polyvinyl chloride resins are used. Thermoplastic resins are not desirable, and it is desirable to use non-halogen-based thermoplastic resins. In particular, from the viewpoints of various physical properties, processability, versatility, economical efficiency, etc., it is most desirable to use a polyolefin-based resin or polyester-based resin (amorphous or biaxially stretched) as the non-halogen-based resin. thermoplastic resin.

What is necessary is just to select and use suitably as a polyolefin resin from the many types already listed, according to the use purpose etc. of a decorative sheet. In particular, polypropylene-based resins, ie, homopolymers or copolymers containing propylene as a main component, are most suitable for general use. For example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, etc. can be used alone or in a suitable blend, or a resin obtained by further blending heteroarranged polypropylene with them appropriately, etc. can be used. In addition, it may be a copolymer containing an olefin-based monomer other than propylene, and for example, it can be exemplified by having a polypropylene crystal part and containing 15 mol% or more of α-olefins other than propylene having 2 to 20 carbon atoms, preferably A propylene-α-olefin copolymer or the like of one or more of ethylene, butene-1,4-methylpentene-1, hexene-1, or octene-1 comonomers. In addition, low-density polyethylene, ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, styrene- Modifiers for butadiene copolymers or their hydrogenated products.

In addition, to the colored layer 12, for example, colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, One or more kinds of additives among various additives such as antifungal agents, friction reducing agents, light scattering agents, and gloss modifiers.

The thickness of the colored layer 12 is preferably within a range of 40 μm or more and 150 μm or less, and more preferably 50 μm or more and 130 μm or less. When the thickness of the coloring layer 12 is 40 micrometers or more, it can absorb the unevenness|corrugation of the floor board which becomes a base, a level difference, etc., and the construction completion degree of the decorative sheet 10 becomes favorable. In addition, when the thickness of the colored layer 12 is 150 μm or less, the manufacturing cost of the decorative sheet 10 can be reduced without forming the colored layer 12 to a thickness greater than necessary.

(pattern pattern layer) The pattern pattern layer 13 is formed on the colored layer 12, and is provided as a layer for adding a pattern for imparting design properties. The pattern pattern layer 13 may be omitted when it can be substituted for the coloring of the colored layer 12 . The pattern layer 13 is formed using printing ink, paint, or the like prepared by dissolving or dispersing a colorant such as a dye or a pigment in an appropriate dilution solvent together with an appropriate binder resin. The printing ink, paint, and the like can be applied by, for example, various printing methods such as gravure printing and lithography, various coating methods such as gravure coating and roll coating, and the like. In addition, as the binder resin, for example, urethane-based resin, acrylic-based resin, chlorinated vinyl acetate-based resin, polyimide-based resin, nitrocellulose, etc., or a mixture thereof can be used. etc, but of course not limited to them. Further, as the pattern, any pattern can be used, for example, a wood grain pattern, a stone pattern, a cloth pattern, an abstract pattern, a geometric pattern, a letter, a symbol, a monochromatic pattern, etc., or a combination thereof, etc. can be used. In addition, in order to improve the concealment of the decorative sheet 10, a concealment layer formed of opaque printing ink or paint containing many opaque pigments such as titanium dioxide and iron oxide may be provided between the pattern layer 13 and the coloring layer 12.

The thickness of the pattern pattern layer 13 is preferably in the range of 1 μm or more and 10 μm or less. When the thickness of the pattern pattern layer 13 is 1 μm or more, printing can be performed clearly. When the thickness of the pattern pattern layer 13 is 10 μm or less, the printing workability at the time of manufacturing the decorative sheet 10 is improved, and the manufacturing cost can be suppressed.

In addition, in order to impart various functions to the pattern pattern layer 13, for example, an extender pigment, a plasticizer, a dispersant, a surfactant, an adhesion imparting agent, an adhesive agent, a drying agent, a curing agent, a curing accelerator, and a curing agent may be added. Functional additives such as retarders.

In addition, the pattern layer 13, for example, may have the color of the substrate to which the decorative sheet 10 is attached. A coloring layer in which the pattern is concealed and painted over the entire surface, and a pattern pattern layer for adding a pattern for design.

(Surface Protective Layer) The surface protective layer 14 is a layer formed on the pattern layer 13 and provided to impart functions such as weather resistance, scratch resistance, stain resistance, and designability to the decorative sheet 10 . The surface protective layer 14 may be a single layer, or a plurality of layers may be stacked to form the surface protective layer 14 . As shown in FIG. 1 , the decorative sheet 10 of the present embodiment is provided with two layers of the first surface protection layer 14 a and the second surface protection layer 14 b as the surface protection layer 14 . When the surface protective layer 14 has a structure (single-layer structure) composed of one layer, the first surface protective layer 14 a becomes the surface protective layer 14 .

The method for forming the surface protective layer 14 including the first surface protective layer 14a and the second surface protective layer 14b is to form the respective layers using a known coating apparatus, thermal drying apparatus and ultraviolet irradiation apparatus according to the type of curable resin. The coating and curing of the coating film are performed to form the surface protective layer 14 .

The surface protective layer 14 plays an important role in determining the advantages and disadvantages of bending workability, weather resistance, scratch resistance, and cleaning performance. The surface protective layer 14 is mainly composed of a curable resin (curable resin). That is, it is preferable that the resin component consists essentially of a curable resin. The term "substantially" means, for example, 80 parts by mass or more when the entire resin is used as 100 parts by mass. The surface protective layer 14 may contain weathering agents, plasticizers, stabilizers, fillers, dispersants, dyes, colorants such as pigments, solvents, ultraviolet absorbers, heat stabilizers, light stabilizers, anti-sticking agents, etc., as required. Various additives such as adhesives, catalyst scavengers, colorants, light scattering agents, and gloss modifiers.

[1st surface protective layer] The first surface protective layer 14a is the layer (the outermost layer) located on the outermost surface (outermost surface) among the layers (the first surface protective layer 14a and the second surface protective layer 14b ) constituting the surface protective layer 14 . In the present embodiment, the first surface protective layer 14a contains at least one of a thermosetting resin, an ultraviolet curing resin, or an electron beam curing resin. In addition, electron beam curable resin and ultraviolet curable resin are collectively described as ionizing radiation curable resin. The first surface protective layer 14a can generally be formed by applying a reactive resin to form a coating film, and then curing the coating film by heating and ionizing radiation irradiation. In the first surface protective layer 14a, there are also differences in characteristics due to differences in curing methods. For example, in general, the first surface protective layer 14a formed of an ionizing radiation curable resin tends to have a high degree of crosslinking after a curing reaction, and thus has high hardness and excellent scratch resistance. On the other hand, the first surface protective layer 14a formed of a thermosetting resin has a low degree of crosslinking, and therefore tends to be low in hardness and excellent in flexibility such as bending and conformability to a substrate.

The first surface protective layer 14a may be a main component of any of a thermosetting resin, an ultraviolet curing resin, or an electron beam curing resin. That is, the main component of the first surface protective layer 14a may be a thermosetting resin monomer, an ultraviolet curing resin or an ionizing radiation curing resin monomer.

For example, when the decorative sheet 10 is used as a member for doors and windows and partitions with many complex shapes, flexibility (for example, suitability for workability) is often required. Therefore, it is preferable to use a thermosetting resin as the main component of the first surface protective layer 14a in the decorative sheet 10 used for, for example, doors, windows and partitions. In addition, when the decorative sheet 10 requires more scratch resistance than flexibility, it is preferable to use an ionizing radiation curable resin.

Further, the main component of the first surface protective layer 14a may be a mixture of a thermosetting resin, an ultraviolet curing resin, and an electron beam curing resin. When this mixture is used as the main component, the ratio of the thermosetting resin, the ultraviolet curing resin, or the electron beam curing resin in the first surface protective layer 14a can be controlled according to the application, so that it can be adjusted according to the requirements of each application. Use decorative sheet 10.

For example, when the decorative sheet 10 is used for doors, windows and partitions, it is preferable to contain a mixture of thermosetting resin, ultraviolet curing resin, and electron beam curing resin that are the main components of the first surface protective layer 14a. Most are thermosetting resins. Specifically, the amount of the thermosetting resin in the mixture may be more than 50% by weight, preferably 70% by weight or more, more preferably 75% by weight or more, and still more preferably 80% by weight or more.

Further, for example, when the decorative sheet 10 is required to have scratch resistance, it is preferable that the mixture of the thermosetting resin, the ultraviolet curing resin and the electron beam curing resin, which are the main components of the first surface protective layer 14a, contain the most is at least one of an ultraviolet curable resin or an electron beam curable resin. Specifically, the content of the ultraviolet curable resin or electron beam curable resin in the mixture may be more than 50 wt %, preferably 70 wt % or more, more preferably 75 wt % or more, still more preferably 70 wt % or more 80% by weight or more.

In this way, since the main component of the first surface protection layer 14a corresponding to the outermost layer of the surface protection layers 14 is a mixture of a thermosetting resin, an ultraviolet curing resin and an electron beam curing resin, it is possible to satisfy the scratch resistance. At the same time, it becomes difficult to cause whitening and cracking of the surface protective layer 14 during bending. However, the performance of the decorative sheet 10 such as scratch resistance and workability as described above does not depend only on the difference in the curing method of the resin used for the first surface protective layer 14a. The performance of the decorative sheet 10 (scratch resistance and processability here), the material design of the resin itself, the addition of additives such as fillers, that is, the physical properties of various components contained in the surface protective layer 14 considerably contribute to the performance. Therefore, the design of the entire surface protective layer 14 has gradually become important.

[Ionizing radiation curable resin] Here, the ionizing radiation curable resin (including ultraviolet curable resin and electron beam curable resin) used for the first surface protective layer 14a is not particularly limited, and a transparent resin mainly composed of the following can be used: The molecule contains a prepolymer (including an oligomer) and/or a monomer containing a radically polymerizable double bond that can be polymerized and crosslinked by irradiation with ionizing radiation such as ultraviolet rays and electron beams. These prepolymers or monomers can be used alone or in combination. The hardening reaction in the ionizing radiation hardening type resin is usually a crosslinking hardening reaction.

Specifically, examples of the above-mentioned prepolymer or monomer include radically polymerizable unsaturated groups such as (meth)acryloyl groups and (meth)acryloyloxy groups, epoxy groups, etc. in the molecule. cationic polymerizable functional group and other compounds. Here, the so-called (meth)acryloyl group means an acryl group or a methacryloyl group.

Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, (Meth)acrylate melamine, tris(meth)acrylate, polysiloxane (meth)acrylate, etc. As these molecular weights, generally about 250 to 100,000 is preferable.

As a monomer having a radically polymerizable unsaturated group, for example, as a monofunctional monomer, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (methyl) Phenoxyethyl acrylate, etc. Moreover, as a polyfunctional monomer, for example, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trihydroxy Methylpropane ethylene oxide tri(meth)acrylate, dipeptaerythritol tetra(meth)acrylate, dipivalerythritol penta(meth)acrylate, dipeptaerythritol hexa(meth)acrylate ) acrylate, etc.

Examples of prepolymers having a cationically polymerizable functional group include epoxy resins such as bisphenol-type epoxy resins and novolak-type epoxy compounds, fatty acid-based vinyl ethers, and aromatic vinyl ethers. Prepolymers of vinyl ether-based resins, etc.

In addition, the above-mentioned prepolymer is also preferably a polyene/thiol-based prepolymer obtained by combining a polyene and a polythiol. Examples of thiols include polythiols such as trimethylolpropane trimercaptoacetate and neotaerythritol tetramercaptoacetate. As a polyene, what added allyl alcohol (allyl alcohol) to both ends of the polyurethane obtained from a diol and a diisocyanate is mentioned, for example.

As the ionizing radiation used for curing the ionizing radiation-curable resin, electromagnetic waves or charged particles having energy to cause a curing reaction of molecules in the ionizing radiation-curing resin (composition) can be used. Usually, ultraviolet rays or electron beams may be used, but visible rays, X-rays, ion beams, and the like may also be used.

As the ultraviolet light source, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, and a metal halide lamp can be used. As a wavelength of an ultraviolet-ray, the range of 190 nm or more and 380 nm or less is normally preferable.

As the electron beam source, for example, various electron beam accelerators such as Cockcroft Walton type, Van de Graff type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type can be used. Among them, those capable of irradiating electrons having an energy in the range of 100 keV or more and 1000 keV or less are particularly preferred, and those capable of irradiating electrons having an energy of 100 keV or more and 300 keV are more preferred.

[Thermosetting resin] Although it does not specifically limit as a thermosetting resin used for the 1st surface protective layer 14a here, For example, a 2-component curable urethane resin is mentioned. The 2-component curable urethane-based resin is not particularly limited, and among them, a polyol component (acrylic polyol, polyester polyol, polyether polyol, cyclic polyol, cyclic polyol, cyclic polyol, polyester polyol, cyclic polyol, etc.) containing an OH group as a main ingredient can be used. Oxygen polyol, etc.), and the isocyanate component (toluene diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate) of the curing agent component. Moreover, as a thermosetting resin, it is not limited to these, A 1-component reaction hardening type polyurethane resin, a 1-component or 2-component reaction hardening type epoxy resin, etc. can be used.

In addition, the surface protective layer 14 is added with a surfactant. The surfactant includes at least one of a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant. By adding a surfactant, the compatibility between the silver-based antiviral agent and the adhesive of the surface protective layer becomes good, and the concentration variation due to the precipitation of the antiviral agent during coating is suppressed. decorative piece.

In addition, the layer thickness of the first surface protective layer 14a is desirably in the range of 3 μm or more and 15 μm or less. When the thickness of the first surface protective layer 14a is 3 μm or more, various resistances such as scratch resistance, abrasion resistance, and weather resistance are improved. If the thickness of the first surface protective layer 14a is 15 μm or less, it is not necessary to use a large amount of resin material more than necessary, and the cost can be reduced.

[antiviral agent] The surface protective layer 14 contains an antiviral agent that improves antiviral properties. The antiviral agent is preferably a silver-based material. As the antiviral agent, antibacterial zeolite, antibacterial apatite, antibacterial zeolite, antibacterial apatite, antibacterial zeolite, antibacterial apatite, antibacterial zeolite, antibacterial zeolite, antibacterial Inorganic antibacterial agents such as zirconia, etc., or as antiviral agents, zinc pyrithione, 2-(4-thiazolyl)-benzimidazole, 10,10-oxybisphetidine can be used , organic nitrogen-sulfur-halogen series, pyridine-2-thiol-oxide, etc., but silver-based antiviral agents are better in terms of antiviral effect. In addition, the antiviral agent may be a configuration in which a silver-based material is supported on an inorganic material. Thereby, the decorative sheet 10 excellent in durability of the antiviral effect can be obtained.

The addition amount of the antiviral agent in the surface protective layer 14 is in the range of 0.2 mass % or more and 10 mass % or less. When the addition amount of the antiviral agent is 0.2 mass % or more, the antiviral agent acts effectively, and the antiviral property improves. When the addition amount of the antiviral agent is 10 mass % or less, the wound resistance improves.

The average particle diameter of the antiviral agent is desirably 0.5 to 2 times the thickness of the surface protective layer 14 . That is, when the average particle diameter of the antiviral agent is φ and the thickness of the surface protective layer is D, it is desirable that the relationship of 0.5D≦φ≦2D holds. When the average particle diameter of the antiviral agent is 0.5 to 2 times that of the surface protective layer 14 , the antiviral properties become good due to the expansion of the contact area with the antiviral agent and the expansion of the surface area of the antiviral agent itself. In addition, the average particle diameter of the antiviral agent is desirably 1 μm or more and 10 μm or less. When the average particle diameter of the antiviral agent is 1 μm or more, the contact area between the surface protective layer 14 and the antiviral agent increases, and the antiviral property becomes good. When the average particle diameter of the antiviral agent is 10 μm or less, the scratch resistance is improved.

Moreover, it is preferable that the peak of the particle diameter of an antiviral agent exists in plural. Specifically, the peak of the particle diameter of the antiviral agent preferably has two peaks, and the two peaks include a first peak within a range of 1 μm or more and 5 μm or less, and a second peak within a range of 5 μm or more and 10 μm or less. crest. Here, the second peak of the particle diameter of the antiviral agent is a larger value than the first peak. By having a plurality of peaks in the particle diameter of the antiviral agent, the packing density of the antiviral agent is further improved, and more antiviral agents can be added. Therefore, the contact area with the antiviral agent is enlarged, and the surface area of the antiviral agent itself is also enlarged, thereby improving the antiviral property.

In addition, in the decorative sheet 10 of the present embodiment, for example, as a measure to improve contamination resistance, a silicon-based component (for example, a silicone resin) or a fluorine-based component may be set on the outermost surface (the first surface protective layer 14 a ) of the decorative sheet 10 . (eg fluororesin).

[Silicone] In the case of using a silicone resin, it is preferable to use modified silicone from the viewpoint of adhesion and compatibility with the surroundings. When the curable resin constituting the first surface protective layer 14a is formed of an ultraviolet curable resin or an electron beam curable resin, the modified silicon is preferably an ionizing radiation-reactive modified silicone resin. In addition, when the curable resin constituting the first surface protective layer 14a is formed of a thermosetting resin, the modified silicon is preferably a thermally reactive modified silicone resin. In addition, in the case where the curable resin constituting the first surface protective layer 14a is formed by a mixture of an ionizing radiation curable resin and a thermosetting resin, the modified silicon preferably contains intermediate ionizing radiation reactivity and thermal reactivity. At least one of the modified silicone resins.

Modified silicon can be classified into reactive modified silicon and non-reactive silicon. Examples of the thermally reactive modified silicon include monoamine-modified silicon, diamine-modified silicon, epoxy-modified silicon, methanol-modified silicon, carboxyl-modified silicon, mercapto-modified silicon, and silanol-modified silicon. , alcohol modified silicon, glycol modified silicon. In addition, as the modified silicon reactive to ionizing radiation, acrylic modified silicon and methacrylic modified silicon can be exemplified. In addition, non-reactive modified silicon, polyether-modified silicon, aralkyl-modified silicon, long-chain alkyl-modified silicon, and higher fatty acid ester-modified silicon can be exemplified. In addition, as these modified silicon manufacturers, Shin-Etsu Chemical Industry Co., Ltd., Toray. Dow Corning Co., Ltd., Momentive. Performance. Materials. Japan joint venture, Asahi Kasei Wacker Silicone Co., Ltd., etc.

[Fluororesin] Fluorine resins are known for exhibiting the smallest level of surface tension and are suitable as contamination-resistant materials. Examples of the fluororesin contained in the first surface protective layer 14a include tetrafluoroethylene resins, tetrafluoroethylene-ethylene copolymers, polyvinylidene fluoride, and the like, and many derivatives can also be used. . In addition, as manufacturers of these fluororesins, Daikin Industrial Co., Ltd., Mitsui. DUPONT FLUOROCHEMICALS Co., Ltd., etc. The amount of the fluororesin contained in the first surface protective layer 14a is preferably 10 parts by mass or more and 100 parts by mass or less. More preferably, it is 20 parts by mass or more. Here, the fluororesin itself may be a curable resin. That is, part of the fluororesin may also serve as part of the curable resin that is the main component of the surface protective layer 14 (the first surface protective layer 14a, the second surface protective layer 14b). For example, all the resin components of the second surface protective layer 14b may be fluororesins.

In this way, in the decorative sheet 10 of the present embodiment, the outermost layer of the surface protective layer 14 , that is, the first surface protective layer 14 a may contain at least either a silicon-based component or a fluorine-based component. Thereby, the stain resistance of the decorative sheet 10 can be improved. When the contamination resistance is improved, the virus can be suppressed from being present on the surface of the decorative sheet 10 for a long period of time, and as a result, the virus resistance can be further improved.

In addition, in order to improve the adhesive strength of each layer of the decorative sheet 10, an adhesive layer containing a two-part curable urethane-based adhesive using an isocyanate-based hardener may be provided between the pattern layer 13 and the surface protective layer 14.

[Second surface protective layer] The second surface protective layer 14b is a layer (inner layer) formed between the outermost layer and the pattern pattern layer 13 among the layers constituting the surface protective layer 14 (the first surface protective layer 14a, the second surface protective layer 14b). . In the present embodiment, the second surface protection layer 14b is made of at least one of a thermosetting resin, an ultraviolet curing resin, or an electron beam curing resin, like the first surface protection layer 14a. In addition, since the thermosetting resin, the ultraviolet curable resin, or the electron beam curable resin is the same as the curable resin contained in the 1st surface protective layer 14a, description is abbreviate|omitted. Like the first surface protective layer 14a, the second surface protective layer 14b may contain an antiviral agent and a surfactant. In this case, the antiviral agent contained in the second surface protective layer 14b may be the same material as the antiviral agent contained in the first surface protective layer 14a, and may be the same as the antiviral agent contained in the first surface protective layer 14a. Agents of different materials.

(Variation) A modification of the decorative sheet of the first embodiment will be described with reference to FIG. 2 . FIG. 2 is a schematic cross-sectional view for explaining a configuration example of a decorative sheet 20 based on a modification of the first embodiment. As shown in FIG. 2, in the decorative sheet 10, the embossed part 25 may be formed in the surface of the surface protection layer 14, ie, the surface of the 1st surface protection layer 14a, in order to give the designability given. Concave and convex patterns are usually formed by embossing. The embossing method is not particularly limited. For the embossing, a known monolithic or rotary embossing machine can be used. Examples of the concavo-convex shape of the embossed portion 25 include wood-grain board conduit grooves, slate surface concavo-convex (granite split surface, etc.), cloth surface texture, pear skin texture, sand texture, hairline, and ribbed grooves.

<Effects of the first embodiment> The decorative sheet 10 of the present embodiment has the following effects. (1) The addition amount of the antiviral agent of the decorative sheet 10 of this embodiment is 0.2 mass % or more and 10 mass % or less. According to this structure, it becomes possible to implement|achieve higher antiviral property without affecting the intensity|strength of the whole decorative sheet. (2) The average particle diameter of the antiviral agent of the decorative sheet 10 of the present embodiment is 1 μm or more and 10 μm or less. According to this configuration, the contact area of the antiviral agent is enlarged, and the surface area of the antiviral agent itself is enlarged, so that high antiviral properties can be realized.

<Second Embodiment> (Composition of decorative sheet) The decorative sheet of the second embodiment of the present disclosure will be described with reference to FIG. 3 . FIG. 3 is a cross-sectional view for explaining a configuration example of the decorative sheet 30 according to the second embodiment of the present disclosure.

The decorative sheet 30 is formed on one side of the colored layer 12, and the pattern pattern layer 13, the transparent resin layer 36 and the surface protection layer 14 are laminated in this order. That is, the decorative sheet 30 is different from the decorative sheet 10 of the first embodiment in that it includes the transparent resin layer 36 .

Hereinafter, the transparent resin layer 36 will be described. The layers other than the transparent resin layer 36 (the colored layer 12, the pattern layer 13, and the surface protective layer 14) have the same configuration as the layers of the decorative sheet 10, and therefore their descriptions are omitted.

(transparent resin layer) As shown in FIG. 3 , the transparent resin layer 36 is a layer formed between the pattern pattern layer 13 and the surface protective layer 14 . The thickness of the transparent resin layer 36 is preferably, for example, 30 μm or more and 200 μm or less. When the thickness of the transparent resin layer 36 is 30 μm or more, the scratch resistance of the transparent resin layer 36 to abrasion and damage to the surface of the decorative sheet becomes sufficiently high. In addition, when the thickness of the transparent resin layer 36 is 200 μm or less, the flexibility of the decorative sheet does not become excessively higher than necessary, and even when the floor board to which the decorative sheet is attached is not flat The construction is carried out in a state where it is in close contact with the floor board.

[Resin material] As the resin material constituting the transparent resin layer 36 , for example, a thermoplastic resin can be used similarly to the colored layer 12 . The thermoplastic resin is not particularly limited, and for example, polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, and propylene-α-olefin copolymer can be used and other polyolefin resins, or ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene-(meth)acrylic acid (ester) copolymers, ethylene-unsaturated carboxylic acid copolymers metal neutralized products (ionic compounds) ) and other olefin-based copolymer resins and other polyolefin-based resins, or polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate Polyester, polyethylene terephthalate-isophthalate copolymer, 1,4-cyclohexanedimethanol copolymer polyethylene terephthalate, polyarylate, polycarbonate, etc. Ester resins, acrylic resins such as poly(meth)acrylonitrile, polymethyl(meth)acrylate, polyethyl(meth)acrylate, polybutyl(meth)acrylate, polyacrylamide, etc., 6 - Polyamide resins such as nylon, 6,6-nylon, and 6,10-nylon, styrene resins such as polystyrene, AS resin, and ABS resin, polyvinyl chloride, polyvinyl acetate, and polyvinyl alcohol , polyvinyl acetal, polyvinyl butyral and other vinyl resins, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, ethylene-perfluoroalkyl vinyl ether copolymer fluorine-based resins, etc., or mixtures, copolymers, composites, laminates, etc. of two or more of them.

Here, many thermoplastic resins have been mentioned as thermoplastic resins that can be used for the transparent resin layer 36, but in consideration of the recent rise in social concerns about environmental issues, chlorine (halogen) containing chlorine (halogen) resins such as polyvinyl chloride resins are used. The thermoplastic resin is not ideal, and it is desirable to use a non-halogen-based thermoplastic resin. In particular, from the viewpoints of various physical properties, processability, versatility, economical efficiency, etc., it is most desirable to use a polyolefin-based resin or polyester-based resin (amorphous or biaxially stretched) as the non-halogen-based resin. thermoplastic resin.

What is necessary is just to select and use suitably as a polyolefin resin from the many types already listed, according to the use purpose etc. of a decorative sheet. In particular, polypropylene-based resins, ie, homopolymers or copolymers containing propylene as a main component, are most suitable for general use. For example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, etc. can be used alone or in a suitable blend, or a resin obtained by further blending heteroarranged polypropylene with them appropriately, etc. can be used. In addition, it may be a copolymer containing an olefin-based monomer other than propylene, and for example, it can be exemplified by having a polypropylene crystal part and containing 15 mol% or more of α-olefins other than propylene having 2 to 20 carbon atoms, preferably A propylene-α-olefin copolymer of one or more of ethylene, butene-1,4-methylpentene-1, hexene-1, or octene-1 comonomers, and the like. In addition, low-density polyethylene, ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, styrene- Modifiers for butadiene copolymers or their hydrogenated products.

To the transparent resin layer 36, for example, colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antibacterial agents, etc. One or more of various additives such as mold agents, friction reducing agents, light scattering agents, and gloss modifiers. Further, the transparent resin layer 36 preferably has transparency (colorless and transparent, colored and transparent, translucent) so that the pattern of the pattern pattern layer 13 can be seen through from the surface (upper surface) of the decorative sheet 30 .

Moreover, the transparent resin layer 36 may contain the antiviral agent which improves the antiviral property similarly to the surface protection layer 14. By including the antiviral agent in the surface protective layer 14, the antiviral property can be maintained on the outermost surface of the decorative sheet. By including an antiviral agent in both the transparent resin layer 36 and the surface protective layer 14, even if the transparent resin layer 36 is exposed due to abrasion of the surface protective layer 14, it has antiviral properties. From this, it can be seen that it is more preferable to contain an antiviral agent in both the surface protective layer 14 and the transparent resin layer 36 . In addition, since the antiviral agent has the same structure as the antiviral agent contained in the surface protective layer 14 of the decorative sheet 10, description is abbreviate|omitted.

(Variation) A modification of the decorative sheet of the second embodiment will be described with reference to FIG. 4 . FIG. 4 is a schematic cross-sectional view for explaining a configuration example of a decorative sheet 40 according to a modification of the second embodiment. As shown in FIG. 4 , on the surface of the transparent resin layer 36 , in the decorative sheet 40 , an embossed portion 45 to which an embossing process is applied may be formed in order to impart designability. The concavo-convex shape of the embossed portion 45 is the same as that of the embossed portion 25 using the decorative sheet 20 of the above-mentioned first embodiment. Texture, pear skin pattern, sand pattern, thin line, ten thousand line groove, etc. By forming the embossed portion 45 in the transparent resin layer 36, texture can be imparted to the decorative sheet 40, and designability can be improved.

<Effects of the second embodiment> The decorative sheet 30 of the present embodiment has the following effects in addition to the effects of the first embodiment. (3) The decorative sheet 30 of the present embodiment includes the transparent resin layer 36 . According to this structure, the intensity|strength of the whole decorative sheet can be improved, and a cushioning property can be provided.

<Third Embodiment> The decorative material of the third embodiment of the present disclosure will be described with reference to FIG. 5 . FIG. 5 is a cross-sectional view for explaining a configuration example of the decorative material 50 according to the third embodiment of the present disclosure. (Composition of decorative materials) The decorative material 50 is formed on one side of the colored layer 12, and the pattern pattern layer 13 and the surface protection layer 14 are laminated in this order. On the other side of the colored layer 12, an adhesive layer 57 and a base material 58 for doors and windows/partitions are provided. . That is, the decorative material 50 is different from the decorative sheet 10 of the first embodiment in that it includes the adhesive layer 57 and the base material 58 for doors and windows/partition fittings.

Hereinafter, the adhesive agent layer 57 and the base material 58 for doors, windows and partitions will be described. The layers other than the adhesive layer 57 and the base material 58 for doors and windows/partitions (the colored layer 12, the pattern layer 13, and the surface protective layer 14) have the same structure as the layers of the decorative sheet 10, so the description is omitted. .

(adhesive layer) The adhesive layer 57 is a layer that is applied as necessary in order to improve the adhesiveness with the adhesive, and the adhesive is used on the side opposite to the pattern layer 13 in the colored layer 12 of the decorative material 50 The set substrate is then attached. For example, when the substrate is formed of a wood-based material, as the adhesive, an adhesive such as vinyl acetate emulsion type and 2-component curable urethane type is used. Therefore, the adhesive layer 57 is preferably made of These adhesives are designed to match resins. For example, urethane type, acrylic type, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer type, polyester type, etc. can be used. Particularly preferred are a two-component curable urethane-based primer or the like obtained by blending a polyester polyol and a polyisocyanate. In addition, for example, adding inorganic powders such as silicon oxide, barium sulfate, calcium carbonate, etc., can effectively prevent sticking during coiling and storage, and can improve the adhesive force due to the anchoring effect.

(Substrates for doors, windows and partitions) As the base material 58 for doors, windows and partitions, Nanyang wood plywood, particle board, medium density fiberboard (hereinafter referred to as MDF), ordinary plywood specified in Japanese Agriculture and Forestry Standards, etc. can be used. In addition, a base material containing an olefin-based resin to which wood powder is added can also be used. The thickness of the base material 58 for doors, windows and partitions is preferably about 3 mm or more and 25 mm or less. In addition, the base material 58 for doors, windows and partitions may be metal such as aluminum, resin such as plastic, or a composite material thereof. By forming the base material 58 for doors, windows and partitions, it is possible to provide the decorative material 50 which can suppress the occurrence of scratches due to the heel of the shoe and small stones during heavy walking. Moreover, in the present embodiment, the adhesive layer 57 and the base material 58 for doors and windows/partitions are bonded to the decorative sheet 10, but the decorative sheet 20, the decorative sheet 30, or the decorative sheet 40 may be used instead of the decorative sheet 10. form decorative material.

<Effects of the third embodiment> The decorative material 50 of the present embodiment has the following effects in addition to the effects of the first embodiment and the second embodiment. (4) The decorative material 50 of this embodiment is provided with the adhesive layer 57 and the base material 58 for doors, windows and partitions. According to this configuration, it is possible to suppress the occurrence of scars due to the heel of the shoe and small stones during heavy walking. [Example]

Hereinafter, the present disclosure will be further described in detail by means of the embodiments, but the embodiments do not constitute any limitation to the present disclosure. <Example 1> A colored thermoplastic resin layer composed of an olefin material was used as the base sheet. A wood grain pattern was printed thereon with a gravure printing machine as a pattern pattern layer. Further, on the pattern layer, a transparent sheet made of an olefin material was bonded as a transparent resin layer. At this time, the thickness of the transparent resin layer was 80 μm. Then, a thermosetting resin (UC Clear, manufactured by DIC Graphics Co., Ltd.) was applied with a thickness of 3 μm as an inner layer (second surface protective layer) of the surface protective layer. In addition, a thermosetting resin (UC Clear, manufactured by DIC Graphics Co., Ltd.) was applied with a thickness of 3 μm as the outermost layer (first surface protective layer) of the surface protective layer. At this time, a silver-based inorganic additive (BIOSAIDO TB-B100, manufactured by TAISHO-TECHNOS Co., Ltd.) was blended as an antiviral agent at a solid content ratio of 0.2 mass % to the thermosetting resin of the outermost layer. In addition, the antiviral agent has a structure in which silver ions are supported on an inorganic material. In addition, the average particle diameter (φ) of the antiviral agent was set to 5 μm. At this time, the first peak of the particle diameter of the antiviral agent was set to 3 μm, and the second peak was set to 7 μm. In addition, the average particle diameter (φ) of the antiviral agent with respect to the thickness D (3 μm in this Example) of the outermost layer (first surface protective layer) of the surface protective layer was set to 1.67D. Then, the thermosetting resin is cured by heating. In the above manner, the decorative sheet of Example 1 was produced.

<Example 2> The addition amount of the antiviral agent was changed to 7 parts by mass. Except for this, the decorative sheet of Example 2 was produced in the same manner as in Example 1.

<Example 3> The main component of the outermost layer (first surface protective layer) of the surface protective layer was changed to an ultraviolet curable resin (urethane acrylate resin manufactured by DIC Graphics Co., Ltd.). In addition, the thickness of the outermost layer was changed to 6 μm. Except for this, the decorative sheet of Example 3 was produced in the same manner as in Example 1.

<Example 4> The main component of the outermost layer (first surface protective layer) of the surface protective layer was changed to electron beam curable resin. Except for this, the decorative sheet of Example 4 was produced in the same manner as in Example 1.

<Example 5> The addition amount of the antiviral agent was changed to 10 parts by mass. Except for this, the decorative sheet of Example 5 was produced in the same manner as in Example 1.

<Example 6> The addition amount of the antiviral agent was changed to 14 parts by mass. Except for this, the decorative sheet of Example 6 was produced in the same manner as in Example 1.

<Example 7> The average particle diameter (φ) of the antiviral agent was changed to 1 μm. Except for this, the decorative sheet of Example 7 was produced in the same manner as in Example 2.

<Example 8> The average particle diameter (φ) of the antiviral agent was changed to 10 μm. Except for this, the decorative sheet of Example 8 was produced in the same manner as in Example 2. <Example 9> The first peak of the particle diameter of the antiviral agent was changed to 0.1 μm. Except for this, the decorative sheet of Example 9 was produced in the same manner as in Example 2.

<Example 10> The first peak of the particle diameter of the antiviral agent was changed to 1 μm. Except for this, the decorative sheet of Example 10 was produced in the same manner as in Example 2.

<Example 11> The first peak of the particle diameter of the antiviral agent was changed to 5 μm. Except for this, the decorative sheet of Example 11 was produced in the same manner as in Example 2.

<Example 12> The first peak of the particle diameter of the antiviral agent was changed to 6 μm. Except for this, the decorative sheet of Example 12 was produced in the same manner as in Example 2.

<Example 13> The second peak of the particle diameter of the antiviral agent was changed to 4 μm. Except for this, the decorative sheet of Example 13 was produced in the same manner as in Example 2.

<Example 14> The second peak of the particle diameter of the antiviral agent was changed to 5 μm. Except for this, the decorative sheet of Example 14 was produced in the same manner as in Example 2.

<Example 15> The second peak of the particle diameter of the antiviral agent was changed to 10 μm. Except for this, the decorative sheet of Example 15 was produced in the same manner as in Example 2.

<Example 16> The second peak of the particle diameter of the antiviral agent was changed to 20 μm. Except for this, the decorative sheet of Example 16 was produced in the same manner as in Example 2.

<Example 17> The first peak of the particle diameter of the antiviral agent was changed to 0.1 μm, and the second peak was changed to 4 μm. Except for this, the decorative sheet of Example 17 was produced in the same manner as in Example 2.

<Example 18> The first peak of the particle diameter of the antiviral agent was changed to 10 μm, and the second peak was changed to 20 μm. Except for this, the decorative sheet of Example 18 was produced in the same manner as in Example 2.

<Example 19> The thickness of the surface protective layer was changed to 2 μm. Except for this, the decorative sheet of Example 19 was produced in the same manner as in Example 2.

<Example 20> The thickness of the surface protective layer was changed to 3 μm. Except for this, the decorative sheet of Example 20 was produced in the same manner as in Example 2.

<Example 21> The thickness of the surface protective layer was changed to 15 μm. Except for this, the decorative sheet of Example 21 was produced in the same manner as in Example 2.

<Example 22> The thickness of the surface protective layer was changed to 25 μm. Except for this, the decorative sheet of Example 22 was produced in the same manner as in Example 2.

<Example 23> The thickness of the transparent resin layer was changed to 20 μm. Except for this, the decorative sheet of Example 23 was produced in the same manner as in Example 2.

<Example 24> The thickness of the transparent resin layer was changed to 30 μm. Except for this, the decorative sheet of Example 24 was produced in the same manner as in Example 2.

<Example 25> The thickness of the transparent resin layer was changed to 200 μm. Except for this, the decorative sheet of Example 25 was produced in the same manner as in Example 2.

<Example 26> The thickness of the transparent resin layer was changed to 210 μm. Except for this, the decorative sheet of Example 26 was produced in the same manner as in Example 2.

<Comparative Example 1> In the surface protective layer, the addition of an antiviral agent was omitted. Except for this, the decorative sheet of Comparative Example 1 was produced in the same manner as in Example 28.

<Comparative Example 2> The addition amount of the antiviral agent was changed to 0.1 mass %. Other than that, the decorative sheet of Comparative Example 2 was produced in the same manner as in Example 1.

<Comparative Example 3> The average particle diameter (φ) of the antiviral agent was changed to 0.5 μm. Except for this, the decorative sheet of Comparative Example 3 was produced in the same manner as in Example 2.

<Comparative Example 4> The average particle diameter (φ) of the antiviral agent was changed to 13 μm. Except for this, the decorative sheet of Comparative Example 4 was produced in the same manner as in Example 2.

<Evaluation determination> With respect to the decorative sheets obtained in the above-mentioned Examples 1 to 26 and Comparative Examples 1 to 4, the antiviral performance and the bending workability were evaluated by the following methods. <Evaluation> [Antiviral performance] The antiviral test was carried out according to ISO 21702 with respect to the decorative sheets of Examples 1 to 26 and Comparative Examples 1 to 4. A 50 mm square test sample was placed in a sterilized petri dish, and 0.4 mL of virus liquid was inoculated on the sample. At this time, a virus liquid containing an enveloped virus (influenza virus) was used as the virus liquid. After that, a 40 mm square polyethylene film was covered on the sample. Cover the petri dish at 25°C. The sample and virus are inoculated under the condition of humidity of 90% or more. After a predetermined time (24 hours), 10 mL of SCDLP medium was poured into the petri dish to wash out the virus. The eluate was tested for virus infectivity titer by plaque method. <Determination of viral infectivity (plaque method)> The host cells were cultured in a monolayer on a 6-well plate, and 0.1 mL of the eluate diluted in stages was inoculated into the wells one by one. In 5%CO ₂ . After culturing for 1 hour at a temperature of 37° C. to allow the virus to be absorbed into the cells, the agar culture medium was poured into a 6-well plate, and the cells were further cultured for 2 to 3 days. After culturing, the cells were fixed. Stain, and count the number of plaques formed. <Calculation of virus infection titer> According to the following formula, the virus infection titer per 1 cm ² of the sample was calculated. V=(10×C×D×N)/A V: virus infection titer per 1 cm ² of sample (PFU/cm ² ) C: number of plaques measured D: dilution ratio of wells where plaques were measured N: amount of SCDLP A: Contact area between sample and virus (area of polyethylene film) <Calculation of antiviral activity value> The antiviral activity value was calculated according to the following formula. Here, when the antiviral activity value was 2 log ₁₀ or more, it was determined that there was an antiviral effect. Antiviral activity value=log(Vb)-log(Vc) Log(Vb): common logarithmic value of virus infection titer per 1 ^cm2 of unprocessed sample after 24 hours Log(Vc): Antiviral value per 1 ^cm2 after 24 hours The antiviral activity value calculated by the following three-stage evaluation of ⊚, ∘, and × was used for the common logarithmic value of the virus infection titer of the virus-processed sample. <Evaluation Criteria> ⊚: When the antiviral activity value is 3 log ₁₀ or more ○: When the antiviral activity value is 2 log ₁₀ or more ×: When the antiviral activity value is less than 2 log ₁₀

[Bending processability] On the surface of MDF (broad-leaved tree) with a thickness of 3 mm, which is a base material for doors and windows and partition parts, in a wet state, 100 g/m ² of 2-liquid aqueous emulsion adhesive (manufactured by Chuo Rika Kogyo Co., Ltd.) is applied. After "RIKABOND" (weight ratio BA-10L/BA-11B=100:2.5)) was used as an adhesive, the decorative sheets of Examples 1 to 26 and Comparative Examples 1 to 4 were attached to each other and cured for 24 hours to prepare Examples 1 to 26 and Comparative Examples 1 to 4 as the decorative materials for doors, windows and partitions. V-cut processing is performed on these door, window and partition trim materials. The appearance state was confirmed by visual inspection of the bending apex. As a V-cut process, it is attached to the decorative material for doors and windows and partitions, from the surface side where the decorative sheet is not attached to the boundary where the above-mentioned window and partition base material and the decorative sheet are attached, so that the decorative sheet does not have any The scars' way into the V-groove. Next, the window/partition base material is folded to 90 degrees along the V-shaped groove so that the surface to which the decorative sheet 1 is attached is folded downward. <Evaluation Criteria> ⊚: There were no cracks, whitening, etc. of the surface protective layer at all at the bending apex. ◯: There are almost no cracks, whitening, etc. of the surface protective layer at the folded apex. △: Cracks and whitening of the surface protective layer occurred in only a part of the bending apex. ×: Cracks and whitening of the surface protective layer occurred at the bending apex. The above evaluation results are shown in Table 1.

[Table 1] surface protection layer transparent resin layer Evaluation medial layer top layer antiviral agent Thickness D of the outermost layer (μm) Average particle diameter of antiviral agent relative to thickness D of surface protective layer Thickness (μm) Antiviral properties Suitable for processability Material Material Addition amount (mass %) Average particle size φ (μm) The first peak of particle size (μm) The second peak of particle size (μm) Example 1 Thermosetting resin Thermosetting resin 0.2 5 3 7 3 1.67D 80 ◎ ◎ Example 2 Thermosetting resin Thermosetting resin 7 5 3 7 6 0.87D 80 ◎ ◎ Example 3 Thermosetting resin UV curable resin 7 5 3 7 3 1.67D 80 ◎ ◎ Example 4 Thermosetting resin Electronic beam hardening resin 7 5 3 7 3 1.67D 80 ◎ ◎ Example 5 Thermosetting resin Thermosetting resin 10 5 3 7 3 1.67D 80 ◎ ◎ Example 6 Thermosetting resin Thermosetting resin 14 5 3 7 3 1.67D 80 ○ △ Example 7 Thermosetting resin Thermosetting resin 7 1 3 7 3 0.33D 80 ◎ ○ Example 8 Thermosetting resin Thermosetting resin 7 10 3 7 3 3.33D 80 ◎ ○ Example 9 Thermosetting resin Thermosetting resin 7 5 0.1 7 3 1.67D 80 ○ ◎ Example 10 Thermosetting resin Thermosetting resin 7 5 1 7 3 1.67D 80 ◎ ◎ Example 11 Thermosetting resin Thermosetting resin 7 5 5 7 3 1.67D 80 ◎ ◎ Example 12 Thermosetting resin Thermosetting resin 7 5 6 7 3 1.67D 80 ○ ◎ Example 13 Thermosetting resin Thermosetting resin 7 5 3 4 3 1.67D 80 ○ ◎ Example 14 Thermosetting resin Thermosetting resin 7 5 3 5 3 1.67D 80 ◎ ◎ Example 15 Thermosetting resin Thermosetting resin 7 5 3 10 3 1.67D 80 ◎ ◎ Example 16 Thermosetting resin Thermosetting resin 7 5 3 20 3 1.67D 80 ○ ◎ Example 17 Thermosetting resin Thermosetting resin 7 5 0.1 4 3 1.67D 80 ○ ◎ Example 18 Thermosetting resin Thermosetting resin 7 5 10 20 3 1.67D 80 ○ ◎ Example 19 Thermosetting resin Thermosetting resin 7 5 3 7 2 2.5D 80 ◎ ○ Example 20 Thermosetting resin Thermosetting resin 7 5 3 7 3 1.67D 80 ◎ ◎ Example 21 Thermosetting resin Thermosetting resin 7 5 3 7 15 0.33D 80 ◎ ◎ Example 22 Thermosetting resin Thermosetting resin 7 5 3 7 25 0.2D 80 ◎ ○ Example 23 Thermosetting resin Thermosetting resin 7 5 3 7 3 1.67D 20 ◎ ○ Example 24 Thermosetting resin Thermosetting resin 7 5 3 7 3 1.67D 30 ◎ ◎ Example 25 Thermosetting resin Thermosetting resin 7 5 3 7 3 1.67D 200 ◎ ◎ Example 26 Thermosetting resin Thermosetting resin 7 5 3 7 3 1.67D 210 ◎ ○ Comparative Example 1 Thermosetting resin Thermosetting resin - - - - 3 - 80 × ◎ Comparative Example 2 Thermosetting resin Thermosetting resin 0.1 5 3 7 3 1.67D 80 × ◎ Comparative Example 3 Thermosetting resin Thermosetting resin 7 0.5 3 7 3 0.16D 80 × ◎ Comparative Example 4 Thermosetting resin Thermosetting resin 7 13 3 7 3 4.33D 80 × ◎

As shown in Table 1, from the evaluation results of Examples 1 to 26 and Comparative Examples 1 and 2, it can be seen that compared with the case where the addition amount of the antiviral agent is less than 0.2 mass % as in Comparative Examples 1 and 2, the When the addition amount of the antiviral agent was 0.2 mass % or more as in Examples 1 to 26, the antiviral properties were high.

In addition, from the evaluation results of Examples 1 to 26 and Comparative Examples 3 and 4, it can be seen that the average particle diameter (φ) of the antiviral agent is less than 1 μm and more than 10 μm as in Comparative Examples 3 and 4. Antiviral properties were high when the average particle diameter (φ) of the antiviral agent was 1 μm or more and 10 μm or less as in Examples 1 to 26.

In addition, the decorative sheet and decorative material of the present disclosure are not limited to the above-described embodiments and examples, and various modifications can be made within a range that does not impair the characteristics of the invention.

10, 20, 30, 40: Decorative pieces 12: Shading Layer 13: Pattern layer 14: Surface protection layer 14a: 1st surface protective layer 14b: 2nd surface protective layer 25,45: Embossed part 36: Transparent resin layer 50: Decorative material 57: Adhesive layer 58: Base material for doors and windows and partition accessories

FIG. 1 is a cross-sectional view schematically showing a configuration example of the decorative sheet according to the first embodiment of the present disclosure. FIG. 2 is a cross-sectional view schematically showing a modification of the decorative sheet according to the first embodiment of the present disclosure. 3 is a cross-sectional view schematically showing a configuration example of the decorative sheet according to the second embodiment of the present disclosure. 4 is a cross-sectional view schematically showing a modification of the decorative sheet according to the second embodiment of the present disclosure. 5 is a cross-sectional view schematically showing a configuration example of a decorative material according to a third embodiment of the present disclosure.

10: Decorative piece

12: Shading Layer

13: Pattern layer

14: Surface protection layer

14a: 1st surface protective layer

14b: 2nd surface protective layer

Claims (16)

A decorative sheet, which has: coloring layer, pattern layer, and surface protection layer, The surface protection layer has a first surface protection layer containing an antiviral agent and at least one of a thermosetting resin, an ultraviolet curing resin, or an electron beam curing resin, The addition amount of the antiviral agent relative to the surface protective layer is 0.2 mass % or more and 10 mass % or less, The average particle diameter of the antiviral agent is 1 μm or more and 10 μm or less. The decorative sheet of claim 1, wherein the antiviral agent is a silver-based material. The decorative sheet of claim 1 or 2, wherein the surface protection layer has a second surface protection layer disposed between the first surface protection layer and the pattern layer. The decorative sheet according to any one of claims 1 to 3, wherein the thickness of the first surface protective layer is 3 μm or more and 15 μm or less. The decorative sheet according to any one of claims 1 to 4, wherein the average particle size of the antiviral agent is 0.5 times or more and 2 times or less the thickness of the surface protective layer. The decorative sheet according to any one of claims 1 to 5, wherein the antiviral agent has a plurality of peaks of particle diameter. The decorative sheet according to claim 6, wherein the peak of the particle size of the antiviral agent includes a first peak within a range of 1 μm to 5 μm and a second peak within a range of 5 μm to 10 μm. The decorative sheet of any one of claims 1 to 7, wherein the antiviral agent is carried by an inorganic material. The decorative sheet according to any one of claims 1 to 8, wherein the first surface protective layer comprises at least one of a silicon-based component or a fluorine-based component. The decorative sheet according to any one of claims 1 to 9, wherein the first surface protective layer is further added with a surfactant. The decorative sheet of claim 10, wherein the surfactant comprises at least one of a cationic surfactant, an amphoteric surfactant or a nonionic surfactant. The decorative sheet according to any one of claims 1 to 11, wherein embossing (emboss) is formed on the surface protection layer. The decorative sheet according to any one of claims 1 to 12, comprising a transparent resin layer disposed between the pattern layer and the surface protection layer. The decorative sheet of claim 13, wherein the thickness of the transparent resin layer is 30 μm or more and 200 μm or less. The decorative sheet of claim 13 or 14, wherein embossing is formed on the transparent resin layer. A decorative material comprising: as the decorative sheet of any one of claims 1 to 15, and A base material for doors, windows and partitions attached to the back of the colored layer of the decorative sheet.

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